Enhancing CO₂ selectivity in MOFs through a dual-ligand strategy: Experimental and theoretical insights
Carbon dioxide (CO₂) is a primary greenhouse gas, playing a significant role in global warming and climate change. In response, metal-organic frameworks (MOFs) have emerged as effective materials for CO₂ capture. This study focuses on the synthesis and characterization of mono and heterometallic Cd...
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Elsevier
2025-03-01
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| Series: | Journal of CO2 Utilization |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2212982025000198 |
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| author | Amir Kazemi Akram Karbalaee Hosseini Mahyar Ashourzadeh Pordsari Mohsen Tamtaji Saber Keshavarz Faranak Manteghi Azadeh Tadjarodi Ahad Ghaemi Sohrab Rohani William A. Goddard |
| author_facet | Amir Kazemi Akram Karbalaee Hosseini Mahyar Ashourzadeh Pordsari Mohsen Tamtaji Saber Keshavarz Faranak Manteghi Azadeh Tadjarodi Ahad Ghaemi Sohrab Rohani William A. Goddard |
| author_sort | Amir Kazemi |
| collection | DOAJ |
| description | Carbon dioxide (CO₂) is a primary greenhouse gas, playing a significant role in global warming and climate change. In response, metal-organic frameworks (MOFs) have emerged as effective materials for CO₂ capture. This study focuses on the synthesis and characterization of mono and heterometallic Cd and Zn MOFs [Zn₂(DPTTZ)(OBA)₂] (IUST-2), [Cd(DPTTZ)(OBA)] (IUST-3), and [Cd₂Zn(DPTTZ)₀.₅(OBA)₃(H₂O)(HCOOH)] (IUST-4). A dual-ligand strategy was employed using 4,4′-oxybis(benzoic acid) (OBA) and 2,5-di(pyridine-4-yl)thiazolo[5,4-d]thiazole (DPTTZ), with OBA acting as a rigid linker and DPTTZ providing nitrogen and sulfur heteroatoms to enhance gas adsorption. The presence of thiazole rings improves CO₂ selectivity through π-electron interactions and coordination with metal centers, contributing to higher adsorption efficiency. A sonochemical method was used to synthesize the MOFs, ensuring fast, eco-friendly production with uniform crystal growth. Among the synthesized MOFs, IUST-4 exhibited the highest CO₂ adsorption capacity, capturing 168 cm³ /g at 25°C. This superior performance is attributed to the synergistic interaction of Cd and Zn, which strengthens the coordination between CO₂ molecules and open metal sites. In addition, to validate the data and improve the analysis, theoretical studies indicated moderate interactions between CO₂ and the metal centers. These analyses were confirmed based on the Langmuir isotherm and Elovich kinetic models (R² > 0.95). Furthermore, DFT calculations revealed that IUST-4 exhibits the highest adsorption energy (-0.11 eV), outperforming IUST-2 (-0.06 eV) and IUST-3 (-0.05 eV). Additionally, IUST-4 maintained 86.1 % efficiency after ten adsorption-desorption cycles, demonstrating its stability and potential for industrial CO₂ capture applications. Overall, these findings highlight the potential of IUST-4 as a highly effective material for advancing CO₂ capture technologies in industrial applications. |
| format | Article |
| id | doaj-art-3fd7ac5abeb34b6f823835110163d763 |
| institution | Kabale University |
| issn | 2212-9839 |
| language | English |
| publishDate | 2025-03-01 |
| publisher | Elsevier |
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| series | Journal of CO2 Utilization |
| spelling | doaj-art-3fd7ac5abeb34b6f823835110163d7632025-02-09T05:00:17ZengElsevierJournal of CO2 Utilization2212-98392025-03-0193103035Enhancing CO₂ selectivity in MOFs through a dual-ligand strategy: Experimental and theoretical insightsAmir Kazemi0Akram Karbalaee Hosseini1Mahyar Ashourzadeh Pordsari2Mohsen Tamtaji3Saber Keshavarz4Faranak Manteghi5Azadeh Tadjarodi6Ahad Ghaemi7Sohrab Rohani8William A. Goddard9Research Laboratory of Inorganic Chemistry and Environment, Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114, Iran; Department of Chemical and Biochemical Engineering, Western University, London, ON N6A 5B9, CanadaResearch Laboratory of Inorganic Materials Synthesis, Department of Chemistry, Iran University of Science and Technology (IUST), Tehran 16846-13114, IranSchool of Chemical, Petroleum and Gas Engineering, Iran University of Science and Technology, Tehran 16846-13114, IranDepartment of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran, IranResearch Laboratory of Inorganic Chemistry and Environment, Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114, IranResearch Laboratory of Inorganic Chemistry and Environment, Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114, Iran; Corresponding authors.Research Laboratory of Inorganic Materials Synthesis, Department of Chemistry, Iran University of Science and Technology (IUST), Tehran 16846-13114, Iran; Corresponding authors.School of Chemical, Petroleum and Gas Engineering, Iran University of Science and Technology, Tehran 16846-13114, Iran; Corresponding authors.Department of Chemical and Biochemical Engineering, Western University, London, ON N6A 5B9, CanadaMaterials and Process Simulation Center, California Institute of Technology, Pasadena, CA 91125, USACarbon dioxide (CO₂) is a primary greenhouse gas, playing a significant role in global warming and climate change. In response, metal-organic frameworks (MOFs) have emerged as effective materials for CO₂ capture. This study focuses on the synthesis and characterization of mono and heterometallic Cd and Zn MOFs [Zn₂(DPTTZ)(OBA)₂] (IUST-2), [Cd(DPTTZ)(OBA)] (IUST-3), and [Cd₂Zn(DPTTZ)₀.₅(OBA)₃(H₂O)(HCOOH)] (IUST-4). A dual-ligand strategy was employed using 4,4′-oxybis(benzoic acid) (OBA) and 2,5-di(pyridine-4-yl)thiazolo[5,4-d]thiazole (DPTTZ), with OBA acting as a rigid linker and DPTTZ providing nitrogen and sulfur heteroatoms to enhance gas adsorption. The presence of thiazole rings improves CO₂ selectivity through π-electron interactions and coordination with metal centers, contributing to higher adsorption efficiency. A sonochemical method was used to synthesize the MOFs, ensuring fast, eco-friendly production with uniform crystal growth. Among the synthesized MOFs, IUST-4 exhibited the highest CO₂ adsorption capacity, capturing 168 cm³ /g at 25°C. This superior performance is attributed to the synergistic interaction of Cd and Zn, which strengthens the coordination between CO₂ molecules and open metal sites. In addition, to validate the data and improve the analysis, theoretical studies indicated moderate interactions between CO₂ and the metal centers. These analyses were confirmed based on the Langmuir isotherm and Elovich kinetic models (R² > 0.95). Furthermore, DFT calculations revealed that IUST-4 exhibits the highest adsorption energy (-0.11 eV), outperforming IUST-2 (-0.06 eV) and IUST-3 (-0.05 eV). Additionally, IUST-4 maintained 86.1 % efficiency after ten adsorption-desorption cycles, demonstrating its stability and potential for industrial CO₂ capture applications. Overall, these findings highlight the potential of IUST-4 as a highly effective material for advancing CO₂ capture technologies in industrial applications.http://www.sciencedirect.com/science/article/pii/S2212982025000198MOFDual-ligand strategyCO2 captureSelectivityDFT calculation |
| spellingShingle | Amir Kazemi Akram Karbalaee Hosseini Mahyar Ashourzadeh Pordsari Mohsen Tamtaji Saber Keshavarz Faranak Manteghi Azadeh Tadjarodi Ahad Ghaemi Sohrab Rohani William A. Goddard Enhancing CO₂ selectivity in MOFs through a dual-ligand strategy: Experimental and theoretical insights Journal of CO2 Utilization MOF Dual-ligand strategy CO2 capture Selectivity DFT calculation |
| title | Enhancing CO₂ selectivity in MOFs through a dual-ligand strategy: Experimental and theoretical insights |
| title_full | Enhancing CO₂ selectivity in MOFs through a dual-ligand strategy: Experimental and theoretical insights |
| title_fullStr | Enhancing CO₂ selectivity in MOFs through a dual-ligand strategy: Experimental and theoretical insights |
| title_full_unstemmed | Enhancing CO₂ selectivity in MOFs through a dual-ligand strategy: Experimental and theoretical insights |
| title_short | Enhancing CO₂ selectivity in MOFs through a dual-ligand strategy: Experimental and theoretical insights |
| title_sort | enhancing co₂ selectivity in mofs through a dual ligand strategy experimental and theoretical insights |
| topic | MOF Dual-ligand strategy CO2 capture Selectivity DFT calculation |
| url | http://www.sciencedirect.com/science/article/pii/S2212982025000198 |
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